Trisazo dyes and process of preparing the same



Patented Jan. 13, 1931 UNITED STATES nanny JORDAN, or wmameron, DELAWARE, assrcnoa TO 1:. I. no rom' 1m nnmooas a cor rm, or WILMINGTON, DELAWARE, A CORPORATION or DELA- WARE TRIS A DYES AND PROCESS OF PREPARING THE SAME llo Drawing.

This invention relates to blue trisazo dyes for cotton and to the method of preparing the same. These dyes show a very good fastness to light and are prepared by diazotizing A a 1-amino-8-naphthol-disulphonic acid having only one sulpho group in each nucleus, coupling the diaz-o compound to an amino compound having a free para-position and not containing a free hydroxyl-, sulphoor second amino roup, diazotizing the aminoazo compoun coupling it to 2-a'mino-5- naphthol-T-sulphonic acid, then diazotizing this disazo dye and coupling it to a coupling component of the naphthalene series having u at least one hydroxy group. The acid dyes have probably the following general formula sawnts R, being an aromatic radical not containing a free hydroxy1-, sulpho or amino-group and R being a coupling component of the naphthalene series having at least one hydroxyl group.

The new dye compounds and their prepara tion are disclosed in the following examples of actual embodiments of the process. It is to be understood that these examples are furnished by way of illustration only, and that the details of the procedure specified therein, as well as the particular proportions, reagents, temperatures, etc., are susceptible of variation and substitution. I

Ewample 1.341 parts of l-amino-S-naphthol-3 tfi-disulphonic acid (H-acid) are diazotized in the usual way andto the diazo there is added a solution of 144 parts alpha-naphthylamine in 2500 parts of water and 150 parts of a 31% hydrochloric acid solution dissolved at 8590 C. The coupling temperature is kept at 1520 0., the mineral acid reaction being neutralized with sodium acetate. The coupling will be complete within about one hour. It is then made alkaline with sodium hydroxide, acidified again with Application filed August 28, 1928. Serial No. 302,645.

hydrochloric acid and diazotized at 6-5"; G.

with a solution of 69 parts of sodium nitrite.

The diazotization will be complete in ten minutes and is then coupled with a solution of 239 parts'of 2-amino-5-naphthol-7-sulphonic acid at 0 5 C. containing sufiicient' sodium carbonate to maintain a strong alluv line reaction during the coupling. The

bluish-violet dye is salted out and filteredf The paste is stirred up with 4000 parts of water, cooled to 10 (3., acidified with 350 parts of a 31% hydrochloric acid solution and diazotized with a solution of 69 parts of so-,

dium nitrate. The diazotiz'ation will be complete within one-half hour. It is then coupled to a solution of 224 parts of l-naphthol- 4-sulphonic acid containing 500 parts of sodium carbonate at atemperature of O5 (1..

This final coupling is heated to C. and salted out. The new dye is soluble in water with a bright blue coloration and dye cotton and other vegetable fibers in bright reddishblue shades which show an excellent fastness to light. The acid dye probably has the following formula.

on coin SO'H N=N Example 2.-Replacin in Example 1 the last component (1 -nap hthol 1- S111 honic acid) by 341 parts of 1-arnino-8-nap thol- 3:6-disulphonic acid, leaving all the other conditions the same, a dye will be obtained which is soluble in water with a very bright greenish-blue coloration, dyeing cotton in bright greenish-blue shades of excellent fastness to li ht. The acid dye probably has the following formula:

on '5 0.11 on N=N N=N SOaH N=N soar son;

Example 3.Stsbstituting, Example 2, the

IUD

second component alpha-naphthylamine) by 137 parts of cresi ine OOH:

leavin all other conditions the same a dye is obtained the shade of which is very slightly redder than the one of Examp e 2, but having the same pro erties. The acid dye probably has the fol owing formula:

on N=N OH N=N s 0.1: s 0.11

0 H soiu- N=N s o. n sons 0 s,

For the first component other eri-aminonaphthol-disulphonic acids can used, as 1 8 :4: 6, 1 :8: 3: o-amino naphthol disulphonic acids. As second components other amino compounds can he used as m-toluidine, p-xylidine, and others. As last components other coupling components of the naphthalene series may be used, as 2: 6, 2 :7 and 1: o-naphthol-sulphonic acids, alphaand beta-naphthol-disulphonic acids, diox naphthalene-monoand disul honic aci s and amino-naphthol-monoan disulphonic acids.

In spite of the fact that trisazo d es coitaining a hydroxyl group in a mid 1e component are generally of a dull shade and of inferior fastness to light as compared to trisazo dyes without a hydroxyl group in any of the middle components, the dyes of the present invention have been foun to be of unusual brightness and fastness to light.

It will be obvious that by varyin the reagents employed a large number 0 dyes may be made within the scope of the appended claims. These dyes are all characterized by an unusual afiinit for textiles, pspficially cotton, and an excellient fastness to I claim:

1. A dye compound having the general formula:

where R represents a residue of a l-amino- 8 naphthol disulphonic acid having only one sulpho group in each nucleus, R represents an aromatic radical not containing a free group of the class consisting of hydroxyl, sulpho and amino groups, and R represents a radical of a coupling component of the naphthalene series having at least one hydroxyl group.

2. A dye compound having the general formula:

where R represents a residue of a compound of the class consisting of 1:8:3z6, 1:8:4:6 and 1 8 3: fi-amino-naphthol-disulphonic acids, R represents a radical of a compound of the class consisting of alpha-naphthylamine, m-toluidine, p-xylidine, and R represents a radical of a compound of the class consisting of 1:4, 2:6 2:7 and 1:5-naphtholsulphonic acids, alp a and beta naphthol disulphonic acids, dioxy-naphthalene-monoand disulphonic acids and amino-naphtholand disul honic acids.

3. The ye compound set forth in claim 1 wherein R represents a residue of l-amino- 8-naphthol-3 G-disulphonic acid.

4. The d e compound set forth in claim 1 wherein ii, represents a residue of alpha naphthylamine.

5. A d e compound set forth in claim 1 wherein represents a naphthol-sulphonic acid radical.

6. A dyie compound set forth in claim 1 wherein 2 represents an amino-naphtholdisulphonic acid radical. V

7. A dye compound having the formula:

8. The process of preparing a trisazo dye which comprises diazotizing a l-amino-S- na hthol-disulphonic acid having only one su pho group in each nucleus, coupling the diazo comfound to a mono-amino compound having a ree para position and not containing a free gi'ou of the class consisting of hydroxyl and su pho groups, diazotizing the amino-azo compound, couplin it to 2-amino- 5-na1phthol-7 sulphonic acid, iazotizing the resu ting disazo compound and coupling to a compound of the naphthalene series having at least one hydroxyl group.

9. The process of preparing a trisazo d e which comprises diazotizing 1-amino-8-nap thol-3: fi-disulphonio acid, coupling the diazo compound to alpha-naphthylamine, diazotizing the amino-azo compound, coupling it to 2-amino-5-naphthol-7-sulphonic acid, diazotizing the resultin disazo compound and coupling it to a napht ol-sulphonic acid.

10. The process of preparing a trisazo dye which comprises diazotizing l-amino-S-naphthol-3 6-disulphonic acid, coupling the diazo compound to alpha-naphthylamine, diazotizcouplin 2-amino-5-naphtho1-7-sulphonic acid, dlazotizing the resulting disazo com und and conp1i ng it to an amino-mph ol-disulphonic acld.

11. The process of preparing a trisazo d e which com risesdi "n I-amino-S-nap th0l-3iZ6-d1Su1Ph0ni0fl0i H the diazo compound to alpha-nap thy e, diam tizing the amino-azo compound, coupling it to Q-amino-5-naphthol-7-sulphonic acid, diazotizing the resulting djsazo compound and it to 1:8-amino-naphthol-3z6-disulphomc acid.

12. Textile fabric dyed with the compound set forth in claim 1.

In testimony whereof, I aflix my si tm'e.

' HENR YJO AN.

meme-r ing the amino-azo compound, eon 2-amino-5-naphthol-7-sulphonic acid, o-

tizing the resulting disazo com and and conpl rdxg it to an amino-naph ol-disulphonic ael NBY JOB AN.

itto

(Seal) CERTIFICATE or CORRECTION.

Patent No. 1,788,797.

HENRY JORDAN.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line 15, for the word "hydroxy" read hydroxyl; line 64, for the word "nitrate" read nitrite, and line 71, for the word "dye" read dyes; and that the said Letters Patent should be read with these corrections therein that thesame mey conform to the reeordof the'caee inothe Patent Office.

Signed and sealed this 10th day of February, A. D. 1931.

M. J. Moore, Acting Commissioner of Patents.

Grated Januery 13, 1931; to v CERTIFICATE OF CORRECTION.

Patent No. l,788.797. Granted January 13, 193], to

HENRY JORDAN.

it is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line l5, lor the word "hydroxy" read hydroxyl; line 64, for the word "nitrate" read nitrite, and line 7i, for the word "dye" read dyes; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case inthe Patent Office.

Signed and sealed this 10th day of February, A. D. 1931.

M. J. Moore, (Sell) Acting Commissioner of Patents. 

